Synthetic studies on prostanoids 1 synthesis of methyl 9-oxoprostanoate

Saito, Kiyoshi; Ide, Junya; Oda, Osamu; Nakamura, Norio

doi:10.1016/s0040-4039(01)84569-x

Cited by 151 publications

(78 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[2] The transition metal-catalyzed hydroacylation reaction involves the activation of the C À H bond of an aldehyde followed by insertion of an olefin to furnish a ketone function. The first example of an intramolecular hydroacylation reaction was reported by Sakai in 1972, who used Wilkinsons catalyst [RhClA C H T U N G T R E N N U N G (PPh 3 ) 3 ] for the cyclization of 4-pentenals into cyclopentanones. [3,4] A major drawback of this reaction is the competitive decarbonylation of the corresponding acyl-metal intermediates, forming reduced substrates.…”

Section: Introductionmentioning

confidence: 99%

“…The first example of an intramolecular hydroacylation reaction was reported by Sakai in 1972, who used Wilkinsons catalyst [RhClA C H T U N G T R E N N U N G (PPh 3 ) 3 ] for the cyclization of 4-pentenals into cyclopentanones. [3,4] A major drawback of this reaction is the competitive decarbonylation of the corresponding acyl-metal intermediates, forming reduced substrates. In order to avoid these competing steps, Miller described the use of a saturated ethylene solution, [5] and Bosnich applied a cationic rhodium(I) complex bearing a chelating diphosphine ligand.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

An Unprecedented Rhodium‐Catalyzed Asymmetric Intermolecular Hydroacylation Reaction with Salicylaldehydes

2007

View full text Add to dashboard Cite

An unprecedented enantio-and diastereoselective rhodium-catalyzed intermolecular hydroacylation reaction of salicylaldehydes with norbornenes is reported in which the corresponding aryl ketones are obtained in high diastereomeric and moderate enantiomeric excesses. It was found that monodentate phosphoramidite ligands gave rise to endo products, while bidentate phosphine ligands catalyzed the reaction to form exo products predominantly.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An Unprecedented Rhodium‐Catalyzed Asymmetric Intermolecular Hydroacylation Reaction with Salicylaldehydes

2007

View full text Add to dashboard Cite

show abstract

“…[2,3] Although intramolecular reactions that afford cyclopentanones are well established, [4] access to larger ring systems [5] and intermolecular reactions remain a considerable challenge.[6] We recently described a intermolecular rhodium-catalyzed reaction based on the use of b-Ssubstituted aldehydes. [7] Although this method had advantages over previous protocols, in that the use of alkyl aldehydes under mild reaction conditions (55-65 8C) is permitted, several limitations remained.…”

mentioning

confidence: 99%

A Second‐Generation Catalyst for Intermolecular Hydroacylation of Alkenes and Alkynes Using β‐S‐Substituted Aldehydes: The Role of a Hemilabile P‐O‐P Ligand

et al. 2006

View full text Add to dashboard Cite

Hydroacylation reactions of alkenes and alkynes catalyzed by transition metals are examples of the growing number of transformations which form carbon-carbon bonds based on CÀH-bond activation.[1] In particular, hydroacylation reactions offer an atom-economic entry to a variety of ketonecontaining products. [2,3] Although intramolecular reactions that afford cyclopentanones are well established, [4] access to larger ring systems [5] and intermolecular reactions remain a considerable challenge.[6] We recently described a intermolecular rhodium-catalyzed reaction based on the use of b-Ssubstituted aldehydes. [7] Although this method had advantages over previous protocols, in that the use of alkyl aldehydes under mild reaction conditions (55-65 8C) is permitted, several limitations remained. Paramount among these were the need to use electron-poor alkenes to achieve good reactivity (Scheme 1) and the use of [Rh(dppe)-(acetone) 2 ]ClO 4[4a] as the catalyst. Although this catalyst performs relatively well in intermolecular reactions, the need to generate it immediately before use from the hydrogenation of [Rh(dppe)(nbd)]ClO 4 (nbd = norbornadiene) considerably detracts from its utility.[8] We document herein the development of a highly active hydroacylation catalyst that can be Scheme 1. Intermolecular hydroacylation. dppe = 1,2-bis(diphenylphosphanyl)ethane.

show abstract

“…2) After that, this hydroacylation of 4-alkenals has been expanded to a catalytic process 3,4) and asymmetric reaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] The proposed reaction mechanism is shown in Chart 1.…”

Section: Introductionmentioning

confidence: 99%

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

Oonishi

2015

Chem. Pharm. Bull.

View full text Add to dashboard Cite

Novel Rh(I)-catalyzed cyclizations through a different type of rhodacycle intermediate which is formedby hydroacylation of 4,6-dienal or oxidative addition of diene and alkene are described. Hydroacylation of 4,6-dienal afforded various 7-membered rings in good to high yields, while cycloisomerization of diene and alkene provided 5-or 6-membered rings in good yields. On the basis of these studies, we have also succeeded in developing the sequential reaction of hydroacylation followed by cycloisomerization to produce bicyclic compounds in a stereoselective manner and thus this reaction was expanded to the synthesis of epiglobulol. Furthermore, both Rh(I)-catalyzed hydroacylation and cycloisomerization using ionic liquid (IL) as a solvent were investigated and it was found that the IL recovered after the reaction, which contains the Rh(I) catalyst, could be recycled several times without loss of catalytic activity.

show abstract

Synthetic studies on prostanoids 1 synthesis of methyl 9-oxoprostanoate

Cited by 151 publications

References 4 publications

An Unprecedented Rhodium‐Catalyzed Asymmetric Intermolecular Hydroacylation Reaction with Salicylaldehydes

An Unprecedented Rhodium‐Catalyzed Asymmetric Intermolecular Hydroacylation Reaction with Salicylaldehydes

A Second‐Generation Catalyst for Intermolecular Hydroacylation of Alkenes and Alkynes Using β‐S‐Substituted Aldehydes: The Role of a Hemilabile P‐O‐P Ligand

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

Contact Info

Product

Resources

About